Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
  • H01J61/00—Gas-discharge or vapour-discharge lamps
  • H01J61/02—Details
  • H01J61/38—Devices for influencing the colour or wavelength of the light
  • H01J61/42—Devices for influencing the colour or wavelength of the light by transforming the wavelength of the light by luminescence
  • H01J61/44—Devices characterised by the luminescent material
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
  • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
  • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
  • C09K11/666—Aluminates; Silicates

Definitions

• This invention relates to a method of improving the initial power output and maintenance of ultraviolet-emitting lead-activated barium silicate phosphor used in fluorescent lamps.
• Ultraviolet-emitting phosphors are used in specialty fluorescent lamps for suntanning applications. It has been recognized that various improvements in the performance of phosphors can be obtained if the phosphor material is coated with a protective film or pigment. Such coatings have been applied, for example, by using selective additions to a lamp coating suspension, or by suspending particles of the phosphor in a solution containing the coating material and evaporating the solvent to form coated phosphor particles.
• U.S. Patent 4,691,140 to Sakakibara et al. teaches the use of a fluorescent lamp in which a lead-doped barium silicate phosphor is coated with a continuous metal oxide coating.
• the coating prevents contact between the glass bulb and the phosphor, which has a chemical structure similar to that of glass.
• the interaction of the phosphor with the glass bulb reduces the mechanical strength of the bulb and also reduces the luminous efficiency of the phosphor.
• a method of improving the initial output and maintenance of lead-activated barium silicate phosphor used in fluorescent lamps comprising the steps of: fluidizing particles of a lead-activated barium silicate phosphor powder in a fluidized bed; exposing the fluidized particles to a vaporized coating precursor at a first temperature to at least partially envelop the particles with coating precursor material, the first temperature being less than the temperature at which the coating precursor material decomposes; reacting the coating precursor material enveloping the fluidized particles at a second temperature to form a protective coating over at least a portion of the surface of individual lead-activated barium silicate phosphor particles, the second temperature being greater than or equal to the temperature at which the coating precursor material reacts to form the protective coating; and annealing the coated lead-activated barium silicate phosphor particles at a sufficient temperature for a sufficient time to cause portions of the surface of the individual lead-activated barium silicate phosphor particles to become exposed, whereby the individual lead lead-activated barium silicate phosphor
• the method of the invention involves the formation of a partial protective coating on phosphor particles by gas-phase chemical vapor deposition while the phosphor particles are suspended within a fluidized bed.
• the fluidized particles are exposed to a vaporized precursor material at a first temperature, the first temperature being less than the temperature at which the precursor material decomposes.
• the precursor material is reacted at a second temperature to form a protective coating over at least a portion of the surface of individual phosphor particles, the second temperature being greater than or equal to the temperature at which the precursor material reacts to form the protective coating material.
• the phosphor particles on which the protective coating has thus been formed are then annealed to expose at least a portion of the surface of the individual phosphor particles, thereby forming a partial protective coating on the surface of the individual phosphor particles.
• the fluidized bed is formed by passing an inert gas upwardly through the phosphor particles in order to suspend the particles in the inert gas stream.
• inert gases suitable for use in this method include nitrogen, argon, helium, neon or mixtures thereof.
• the inert gas functions as a carrier gas.
• a volatilizable coating precursor material is vaporized into the inert gas before the inert gas enters the reaction chamber in which the phosphor particles become suspended.
• the carrier gas is saturated with the vapor of the coating precursor material. As the carrier gas containing the vaporized coating precursor material passes upwardly throught the phosphor particles to suspend the particles in the fluidized bed, the particles are enveloped by the vapor of the coating precursor material which is contained in the carrier gas.
• the fluidized bed is preferably maintained in a temperature gradient ranging from a lowest temperature to a highest temperature.
• the lowest temperature should be less than the temperature at which the coating precursor material will decompose, while the highest temperature should be equal to or greater than the temperature at which the coating precursor material reacts to form the protective coating.
• An oxidizing gas if necessary, is introduced into the fluidized bed separately from the carrier gas containing the vaporized coating precursor material.
• suitable oxidizing gases are air or oxygen.
• the oxidizing gas may be mixed with a diluent inert gas.
• the residence time of the phosphor powder particles in the fluidized bed in the method of this invention is significantly less than the time required to form a continuous protective coating over the individual phosphor particles. It has been found that a residence time in the fluidized bed of at least four hours is sufficient to form a complete, continuous protective coating over the phosphor particles. Since only a partial coating is desired, it is essential that the residence time of the phosphor in the fluidized bed be kept to a minimum, say, for 30 minutes to one hour at the most, such that only a partial coating of precursor coating material is formed on the particles. The residence time of the phosphor in the fluidized bed is thus so short that the phosphor powder particles are not completely enveloped by the vaporized precursor coating material.
• the coating precursor material is reacted to form a protective coating on that portion of the phosphor particle surfaces which was enveloped by the vaporized coating precursor material.
• Lead-activated barium silicate phosphor can be sufficiently partially coated after about 30 minutes in the fluidized bed. The partially coated phosphor is then removed from the fluidized bed and transferred to an oven or furnace for annealing.
• the annealing step which follows this reaction step causes the protective coating on the surface of the individual phosphor particles to selectively cover at least a portion of certain sites on the surface of the phosphor particles. It is believed that the annealing step may promote ionic diffusion between the protective coating and the underlying phosphor, causing the resulting partial coating to comprise a mixture of the original coating and a new compound or compounds, such as, for example, aluminum silicate, formed from such ionic diffusion.
• Examples of phosphor coating materials that can be applied by the present method include metal or nonmetal oxides.
• Preferred coating materials are aluminum oxide and silicon dioxide.
• the compound or composition must be volatilizable.
• Organo and alkoxide compounds of the metal or nonmetal of the desired oxide coating material which are volatilizable under the conditions of the method may be used as coating precursor materials in the present invention.
• Acetylacetonates of the metal of the desired oxide coating material can also be used as precursor materials in the present method.
• suitable aluminum oxide precursor materials are represented by the general formula R x (OR') 3-x Al, wherein x is an integer between 0 and 3 inclusive, and R and R' are lower alkyl groups, such as: -CH3; -C2H5; -C3H7; or -C4H9.
• suitable silicon dioxide precursor materials are represented by the general formula R x (OR') 4-x Si, wherein x is an integer between 0 and 4 inclusive, and R and R' are lower alkyl groups, such as -CH3; -C2H5; -C3H7; -C4H9; or -C5H11.
• suitable coating precursor material for aluminum oxide or silicon dioxide coatings is not to be construed as necessarily limiting thereof. Any alkyl, alkoxy, or acetylacetonate compounds of aluminum or silicon which can be vaporized into the inert carrier gas under the conditions of the method may be used as coating precursor material for aluminum oxide coatings or silicon dioxide coatings, respectively.
• Phosphor powders having an average particle size range of about 20 to 80 microns and larger can be fluidized with little or no difficulty. Difficulty is encountered, however, in attempting to fluidize fine phosphor powders, i.e., phosphor powders having an average particle size of less than about 20 microns.
• the difficulty in fluidizing the particles of fine phosphor powder arises from interparticle adhesive forces which cause agglomeration and bridging between the agglomerates. Such agglomeration and bridging of agglomerates normally results in the formation of channels through the bed thereby causing the gas to pass through the channels without fluidizing the particles. Under these circumstances, there is little or no powder bed expansion.
• Particles of fine phosphor powders can be fluidized and coated by the method of the present invention.
• a small amount, up to about 1 weight percent with respect to the phosphor, of a fluidizing aid should be mixed with the phosphor powder to form a uniform mixture.
• an amount of fluidizing aid less than or equal to about 0.05 weight percent with respect to the phosphor is employed.
• Suitable fluidizing aids include small particle size aluminum oxide, e.g., Aluminum Oxide C, or small particle size silica.
• Fluidization of fine phosphor powders can alternatively be accomplished by additional agitation of the phosphor powder particles which are suspended in the stream of carrier gas.
• This additional agitation can be accomplished by various agitating means, such as a mechanical stirrer, and preferably a high speed vibromixer.
• the resulting coating only partially covers the phosphor particle surface. Electron spectroscopy analysis indicates that the barium on the surface of the phosphor will be covered with aluminum oxide before the silica on the surface of the phosphor is covered. This is because lead-activated barium silicate phosphor has two silica ions for each barium ion. Furthermore, barium ions have a greater tendency than silica ions to bond with other ions or compounds because of the stable tetrahedral structure of silica.
• the annealing step is believed to promote ionic diffusion between the silica in the phosphor and the aluminum oxide in the protective coating, possibly causing the formation of a thin layer of a new compound, such as aluminum silicate, as part of the coating of the phosphor. It is this ionic diffusion that causes the aluminum oxide coating to preferentially cover the silica sites on the surface of the phosphor particles. It is believed that the large size of the barium ions tends to inhibit their ionic diffusion.
• the overall effect of this ionic diffusion during the annealing step is that the more mobile ions, such as silica and aluminum, have an affinity for one another, whereas less mobile ions, such as barium, are relatively unaffected, such that the protective aluminum oxide coating preferentially covers more of the silica sites and fewer of the barium sites.
• the protective aluminum oxide coating preferentially covers more of the silica sites and fewer of the barium sites.
• the annealing step is carried out in air at a temperature of from about 700 o C to about 850 o C for a period of from about 15 minutes to about 20 hours.
• the preferred annealing conditions for lead-activated barium silicate phosphor are 780 o C for 4 hours. It is believed that the annealing process causes the aluminum oxide coating on the phosphor particles to preferentially cover silica sites on the phosphor surface, leaving barium sites exposed. This theory is supported by electron spectroscopy analysis which shows a greater degree of barium attentuation before the annealing step.
• the annealing process may remove any moisture present in the aluminum oxide or in the phosphor. It may also improve the adherence of the aluminum oxide coating on the phosphor particle surface. As previously mentioned, ionic migration of silica, aluminum and, to a lesser extent, barium ions may result in the formation of a new compound on the surface of the phosphor.
• the resulting coated, annealed phosphor exhibits improved initial power output and improved maintenance at 100 hours when compared to an uncoated, unannealed phosphor.
• Particles of lead-activated barium silicate phosphor powder were partially coated with aluminum oxide by the method of the present invention.
• a fluidized bed having a quartz tube reactor vessel with a 4-inch inside diameter was used.
• Seven kilograms of lead-activated barium silicate (Sylvania Type 2011, obtained from the Chemical and Metallurgical Division of GTE Products Corporation, Towanda, Pa.) and 7 grams (0.1 weight percent) Aluminum Oxide C, the fluidizing aid (available from DeGussa, Inc.) were dry blended in a polyethylene jar to obtain a uniform dispersion of the Aluminum Oxide C fluidizing aid throughout the barium silicate phosphor powder.
• the mixture of the barium silicate phosphor powder and the fluidizing aid was introduced into the quartz tube reactor vessel.
• Liquid trimethyl aluminum was used in the stainless steel bubbler as the coating precursor material. Nitrogen gas was bubbled into the liquid trimethyl aluminum to form a carrier gas containing vaporized trimethyl aluminum. The resulting vapor-containing gas stream was diluted with additional nitrogen gas and then introduced into the reactor vessel.
• the phosphor powder was heated using 15 liters per minute pure nitrogen as the fluidizing gas.
• the nitrogen was preheated to 50 o C, and the fluidized bed was preheated to 700 o C.
• oxygen was introduced to the reactor at a rate of 8 liters per minute, and the nitrogen flow was reduced to 7 liters per minute.
• 5 liters per minute of the nitrogen was diverted through the bubbler and the vapor-laden bubble exit stream was diluted with 2 liters per minute of pure nitrogen to comprise the fluidizing-coating gas.
• the phosphor was then annealed at 780 o C for 4 hours in air. Electron spectroscopy analysis after the annealing step indicated that none of the barium, and only 17% of the silica, on the surface of the phosphor particles was covered by the aluminum oxide coating.
• the coated, annealed phosphor was then fabricated into 72-inch T12HO (high-output) fluorescent lamps using standard organic suspension methods. These lamps were tested alongside lamps fabricated from the uncoated, unannealed barium silicate phosphor base lot. The initial power output and maintenance data from these lamp tests are indicated in Table I.
• UVA power output for lamps made with the coated, annealed phosphor is up to 4% greater than that of lamps made with the uncoated, unannealed phosphor.
• Maintenance of lamps made with the coated, annealed phosphor is improved by up to 27% over that of lamps made with the uncoated, unannealed phosphor.
• Lamps made with an integrated reflector show greater improvement in both initial power output and maintenance at 100 hours than lamps without an integrated reflector.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Luminescent Compositions (AREA)

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Cited By (5)

Citations (2)

• 1990
  • 1990-12-21 EP EP19900314213 patent/EP0476207A3/de not_active Withdrawn

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